The deposition of corrosion products on the surface of the steel is a key step for understanding the generation of corrosion products. To clarify the molecular mechanism for corrosion product deposition, the reactive molecular dynamics were utilized to study the deposition process of ferric hydroxide (Fe(OH)3) on iron and passivation film substrates. It is shown that the deposition phenomenon mainly occurs on the iron surface, while the surface of the passivation film cannot adsorb Fe(OH)3. Further analysis indicates that the interaction between hydroxyl groups in γ-FeOOH and Fe(OH)3 is very weak, which is unfavorable to the deposition of Fe(OH)3. Moreover, the degree of ordered water in the two systems is affected slightly by deposition but the oxygen in water corrodes Fe(OH)3, breaking its Fe-O bonds, which is more obvious in the Fe system due to its instability. This work has revealed the nanoscale deposition process of corrosion products on the passivation film in a solution environment by reproducing the bonding and breaking of atoms at the molecular level, which is a case in point to the conclusion of the protection of steel bars by passivation film.